DOE OSTI2020
Mo(Pr10Mo22O45)2 crystallizes in the monoclinic Cm space group. The structure is three-dimensional and consists of two molybdenum molecules and one Pr10Mo22O45 framework. In the Pr10Mo22O45 framework, there are fourteen inequivalent Pr3+ sites. In the first Pr3+ site, Pr3+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Pr–O bond distances ranging from 2.34–2.79 Å. In the second Pr3+ site, Pr3+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Pr–O bond distances ranging from 2.33–2.88 Å. In the third Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Pr–O bond distances ranging from 2.30–2.49 Å. In the fourth Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Pr–O bond distances ranging from 2.27–2.51 Å. In the fifth Pr3+ site, Pr3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Pr–O bond distances ranging from 2.34–3.01 Å. In the sixth Pr3+ site, Pr3+ is bonded in a 7-coordinate geometry to eight O2- atoms. There are a spread of Pr–O bond distances ranging from 2.40–3.07 Å. In the seventh Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to eight O2- atoms. There are a spread of Pr–O bond distances ranging from 2.40–3.04 Å. In the eighth Pr3+ site, Pr3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Pr–O bond distances ranging from 2.33–3.01 Å. In the ninth Pr3+ site, Pr3+ is bonded in a 5-coordinate geometry to five O2- atoms. There are a spread of Pr–O bond distances ranging from 2.38–2.73 Å. In the tenth Pr3+ site, Pr3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Pr–O bond distances ranging from 2.37–2.96 Å. In the eleventh Pr3+ site, Pr3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Pr–O bond distances ranging from 2.39–2.95 Å. In the twelfth Pr3+ site, Pr3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Pr–O bond distances ranging from 2.42–3.00 Å. In the thirteenth Pr3+ site, Pr3+ is bonded in a 6-coordinate geometry to eight O2- atoms. There are a spread of Pr–O bond distances ranging from 2.30–2.88 Å. In the fourteenth Pr3+ site, Pr3+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Pr–O bond distances ranging from 2.34–2.91 Å. There are twenty-seven inequivalent Mo+2.67+ sites. In the first Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form corner-sharing MoO5 square pyramids. The corner-sharing octahedra tilt angles range from 45–54°. There are a spread of Mo–O bond distances ranging from 2.13–2.20 Å. In the second Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form corner-sharing MoO5 square pyramids. The corner-sharing octahedra tilt angles range from 48–51°. There are a spread of Mo–O bond distances ranging from 2.13–2.20 Å. In the third Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with two equivalent MoO6 octahedra and corners with two equivalent MoO5 square pyramids. The corner-sharing octahedral tilt angles are 51°. There are a spread of Mo–O bond distances ranging from 2.08–2.18 Å. In the fourth Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with two MoO6 octahedra and corners with two MoO5 square pyramids. The corner-sharing octahedra tilt angles range from 51–55°. There are a spread of Mo–O bond distances ranging from 2.10–2.18 Å. In the fifth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.05–2.15 Å. In the sixth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.06–2.13 Å. In the seventh Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are two shorter (2.15 Å) and two longer (2.16 Å) Mo–O bond lengths. In the eighth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.10–2.17 Å. In the ninth Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with three MoO5 square pyramids, an edgeedge with one MoO6 octahedra, and an edgeedge with one MoO5 square pyramid. There are a spread of Mo–O bond distances ranging from 2.13–2.17 Å. In the tenth Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with three MoO5 square pyramids, an edgeedge with one MoO6 octahedra, and an edgeedge with one MoO5 square pyramid. There are a spread of Mo–O bond distances ranging from 2.09–2.19 Å. In the eleventh Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with three MoO5 square pyramids, an edgeedge with one MoO6 octahedra, and an edgeedge with one MoO5 square pyramid. There are a spread of Mo–O bond distances ranging from 2.11–2.21 Å. In the twelfth Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with two MoO5 square pyramids and an edgeedge with one MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.03–2.17 Å. In the thirteenth Mo+2.67+ site, Mo+2.67+ is bonded to five O2- atoms to form MoO5 square pyramids that share corners with two equivalent MoO5 square pyramids and an edgeedge with one MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.05–2.16 Å. In the fourteenth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.11–2.15 Å. In the fifteenth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.10–2.14 Å. In the sixteenth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.10–2.15 Å. In the seventeenth Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share a cornercorner with one MoO5 square pyramid and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.10–2.26 Å. In the eighteenth Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share a cornercorner with one MoO5 square pyramid and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.06–2.24 Å. In the nineteenth Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share a cornercorner with one MoO5 square pyramid and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.06–2.24 Å. In the twentieth Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with two MoO5 square pyramids, edges with two MoO6 octahedra, and edges with three MoO5 square pyramids. There are a spread of Mo–O bond distances ranging from 2.05–2.17 Å. In the twenty-first Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with two equivalent MoO5 square pyramids, edges with two equivalent MoO6 octahedra, and edges with three MoO5 square pyramids. There are a spread of Mo–O bond distances ranging from 2.10–2.17 Å. In the twenty-second Mo+2.67+ site, Mo+2.67+ is bonded in a distorted T-shaped geometry to three O2- atoms. There are two shorter (2.09 Å) and one longer (2.15 Å) Mo–O bond lengths. In the twenty-third Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with two MoO5 square pyramids and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.09–2.15 Å. In the twenty-fourth Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form MoO6 octahedra that share corners with two equivalent MoO5 square pyramids and edges with four MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.12–2.17 Å. In the twenty-fifth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.06–2.21 Å. In the twenty-sixth Mo+2.67+ site, Mo+2.67+ is bonded in a rectangular see-saw-like geometry to four O2- atoms. There are a spread of Mo–O bond distances ranging from 2.05–2.21 Å. In the twenty-seventh Mo+2.67+ site, Mo+2.67+ is bonded to six O2- atoms to form edge-sharing MoO6 octahedra. There are a spread of Mo–O bond distances ranging from 2.14–2.18 Å. There are fifty-six inequivalent O2- sites. In the first O2- site, O2- is bonded in a 5-coordinate geometry to three Pr3+ and two Mo+2.67+ atoms. In the second O2- site, O2- is bonded in a 5-coordinate geometry to three Pr3+ and two Mo+2.67+ atoms. In the third O2- site, O2- is bonded in a 3-coordinate geometry to three Pr3+ and two Mo+2.67+ atoms. In the fourth O2- site, O2- is bonded in a 3-coordinate geometry to three Mo+2.67+ atoms. In the fifth O2- site, O2- is bonded in a 4-coordinate geometry to one Pr3+ and three Mo+2.67+ atoms. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to three Mo+2.67+ atoms. In the seventh O2- site, O2- is bonded in a 3-coordinate geometry to three Mo+2.67+ atoms. In the eighth O2- site, O2- is bonded to one Pr3+ and three Mo+2.67+ atoms to form distorted corner-sharing OPrMo3 tetrahedra. In the ninth O2- site, O2- is bonded to one Pr3+ and three Mo+2.67+ atoms to form distorted OPrMo3 tetrahedra that share corners with three OPr4 tetrahedra and edges with two equivalent OPr2Mo2 trigonal pyramids. In the tenth O2- site, O2- is bonded in a distorted see-saw-like geometry to two Pr3+ and two Mo+2.67+ atoms. In the eleventh O2- site, O2- is bonded to two Pr3+ and two Mo+2.67+ atoms to form distorted OPr2Mo2 tetrahedra that share corners with two equivalent OPr4 tetrahedra, corners with two OPrMo3 trigonal pyramids, and an edgeedge with one OPr2Mo2 tetrahedra. In the twelfth O2- site, O2- is bonded in a distorted see-saw-like geometry to two Pr3+ and two Mo+2.67+ atoms. In the thirteenth O2- site, O2- is bonded to four Pr3+ atoms to form corner-sharing OPr4 tetrahedra. In the fourteenth O2- site, O2- is bonded to four Pr3+ atoms to form OPr4 tetrahedra that share corners with four OPrMo3 tetrahedra and corners with two equivalent OPr2Mo2 trigonal pyramids. In the fifteenth O2- site, O2- is bonded in a trigonal planar geometry to three Pr3+ atoms. In the sixteenth O2- site, O2- is bonded to four Pr3+ atoms to form corner-sharing OPr4 tetrahedra. In the seventeenth O2- site, O2- is bonded in a distorted see-saw-like geometry to two Pr3+ and two Mo+2.67+ atoms. In the eighteenth O2- site, O2- is bonded in a distorted see-saw-like geometry to two Pr3+ and two Mo+2.67+ atoms. In the nineteenth O2- site, O2- is bonded to two Pr3+ and two Mo+2.67+ atoms to form distorted OPr2Mo2 trigonal pyramids that share corners with four OPr2Mo2 tetrahedra, an edgeedge with one OPrMo3 tetrahedra, and an edgeedge with one OPr2Mo2 trigonal pyramid. In the twentieth O2- site, O2- is bonded in a 3-coordinate geometry to two Pr3+ and two Mo+2.67+ atoms. In the twenty-first O2- site, O2- is bonded in a 3-coordinate geometry to two Pr3+ and two Mo+2.67+ atoms. In the twenty-second O2- site, O2- is bonded in a 3-coordinate geometry to three Pr3+ and two Mo+2.67+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted T-shaped geometry to three Mo+2.67+ atoms. In the twenty-fourth O2- site, O2- is bonded in a 5-coordinate geometry to one Pr3+ and three Mo+2.67+ atoms. In the twenty-fifth O2- site, O2- is bonded in a 5-coordinate geometry to two equivalent Pr3+ and three Mo+2.67+ atoms. In the twenty-sixth O2- si